Accommodating imperfectly aligned memory holes

ABSTRACT

Methods of forming 3-d flash memory cells are described. The methods allow the cells to be produced despite a misalignment in at least two sections (top and bottom), each having multiple charge storage locations. The methods include selectively gas-phase etching dielectric from the bottom memory hole portion by delivering the etchants through the top memory hole. Two options for completing the methods include (1) forming a ledge spacer to allow reactive ion etching of the bottom polysilicon portion without damaging polysilicon or charge-trap/ONO layer on the ledge, and (2) placing sacrificial silicon oxide gapfill in the bottom memory hole, selectively forming protective conformal silicon nitride elsewhere, then removing the sacrificial silicon oxide gapfill before performing the reactive ion etching of the bottom polysilicon portion as before.

CROSS-REFERENCES TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No. 15/882,454, filed on Jan. 29, 2018, which claims the benefit of U.S. Prov. Pat. App. No. 62/456,386, filed Feb. 8, 2017. U.S. patent application Ser. No. 15/882,454 also claims the benefit of U.S. Prov. Pat. App. No. 62/478,508, filed Mar. 29, 2017. The entire disclosures of each of these applications are hereby incorporated by reference in their entirety for all purposes.

FIELD

Embodiments of the invention relate to methods of forming 3-d flash memory.

BACKGROUND

Integrated circuits are made possible by processes which produce intricately patterned material layers on substrate surfaces. Producing patterned material on a substrate requires controlled methods for removal of exposed material. Chemical etching is used for a variety of purposes including transferring a photoresist pattern into underlying layers, thinning layers or thinning lateral dimensions of features already present on the surface. Often it is desirable to have an etch process which etches one material faster than another helping e.g. a pattern transfer process proceed. Such an etch process is said to be selective of the first material. As a result of the diversity of materials, circuits and processes, etch processes have been developed that selectively remove one or more of a broad range of materials.

Dry etch processes are increasingly desirable for selectively removing material from semiconductor substrates. The desirability stems from the ability to gently remove material from miniature structures with minimal physical disturbance. Dry etch processes also allow the etch rate to be abruptly stopped by removing the gas phase reagents. Extremely selective etches have been developed recently to etch silicon nitride, silicon oxide or silicon while retaining the other materials.

A high density VNAND (or 3d-NAND) structure involves many storage layers arranged vertically. Introducing selective etch processes of silicon nitride and silicon oxide into 3d-NAND process flows may enable a greater number of storage layers to be included which may increase the storage density of completed devices. Methods are needed to broaden the utility of selective dry isotropic etch processes in vertical storage devices.

SUMMARY

Methods of forming 3-d flash memory cells are described. The methods allow the cells to be produced despite a misalignment in at least two sections (top and bottom), each having multiple charge storage locations. The methods include selectively gas-phase etching dielectric from the bottom memory hole portion by delivering the etchants through the top memory hole. Two options for completing the methods include (1) forming a ledge spacer to allow reactive ion etching of the bottom polysilicon portion without damaging polysilicon or charge-trap/ONO layer on the ledge, and (2) placing sacrificial silicon oxide gapfill in the bottom memory hole, selectively forming protective conformal silicon nitride elsewhere, then removing the sacrificial silicon oxide gapfill before performing the reactive ion etching of the bottom polysilicon portion as before.

Embodiments disclosed herein include methods of forming a 3-d flash memory cell. The methods include placing a patterned substrate in a substrate processing chamber. The patterned substrate includes a vertical stack of alternating silicon oxide and silicon nitride slabs and a vertical memory hole having sidewalls lined with a conformal ONO layer. The conformal ONO layer includes a first silicon oxide layer, a silicon nitride layer and a second silicon oxide layer. The patterned substrate further includes a first polysilicon layer formed on the conformal ONO layer. The vertical stack includes a bottom portion and a top portion laterally misaligned to form a ledge. The methods further include forming a silicon nitride spacer on the ledge. The methods further include removing a bottom portion of the first polysilicon layer by reactive ion etching the bottom portion of the first polysilicon layer while retaining sidewall portions of the first polysilicon layer. The methods further include removing a bottom portion of the conformal ONO layer using a gas-phase etch. The methods further include removing the silicon nitride spacer from the ledge using a gas-phase etch. The methods further include forming a second polysilicon layer on the first polysilicon layer.

The silicon nitride spacer may completely cover the ledge but may leave a line-of-sight path from top to bottom of the vertical memory hole. Forming the second polysilicon layer may include making electrical contact between the first polysilicon layer, the second polysilicon layer and underlying silicon. The bottom portion and the top portion are laterally misaligned by more than 5 nm. Removing the bottom portion of the conformal ONO layer may be performed by exciting a hydrogen-containing precursor and a fluorine-containing precursor in a remote plasma to form plasma effluents. The plasma effluents may be flowed into a substrate processing region through a showerhead. The patterned substrate may be in the substrate processing region and a temperature of the patterned substrate may be greater than 95° C.

Embodiments disclosed herein include methods of forming a 3-d flash memory cell. The methods include placing a patterned substrate in a substrate processing chamber. The patterned substrate includes a vertical stack of alternating silicon oxide and silicon nitride slabs and a vertical memory hole having sidewalls lined with a conformal ONO layer. The conformal ONO layer includes a first silicon oxide layer, a silicon nitride layer and a second silicon oxide layer. The patterned substrate further includes a first polysilicon layer formed on the conformal ONO layer. The vertical stack includes a bottom portion and a top portion laterally misaligned by more than 5 nm to form a ledge. The methods further include forming sacrificial silicon oxide in the bottom portion of the vertical memory hole. The methods further include forming conformal silicon nitride on exposed portions of the first polysilicon layer uncovered by the sacrificial silicon oxide. The methods further include removing the sacrificial silicon oxide selectively relative to the exposed polysilicon. The methods further include removing a bottom portion of the first polysilicon layer by reactive ion etching the bottom portion of the first polysilicon layer while retaining sidewall portions of the first polysilicon layer. The methods further include removing a bottom portion of the conformal ONO layer using a gas-phase etch. The methods further include removing the conformal silicon nitride. The methods further include forming a second polysilicon layer on the first polysilicon layer and making electrical contact between the second polysilicon layer and underlying silicon.

Removing the conformal silicon nitride may include exciting both a fluorine precursor and an oxygen precursor in a remote plasma and flowing the plasma effluents into the substrate processing region housing the patterned substrate. The fluorine precursor may include nitrogen trifluoride and the oxygen precursor may include molecular oxygen (O₂).

Embodiments disclosed herein include methods of forming a 3-d flash memory cell. The methods include forming a bottom portion of a compound stack of alternating silicon oxide and silicon nitride slabs. The methods further include forming a bottom portion of a memory hole through the bottom portion of the compound stack by patterning the bottom portion of the compound stack. The methods further include filling the bottom portion of the compound stack with doped silicon oxide. The methods further include forming a top portion of the compound stack of alternating silicon oxide and silicon nitride slabs. The methods further include forming a top portion of a memory hole through the top portion of the compound stack by patterning the top portion of the compound stack and exposing the doped silicon oxide. The methods further include selectively removing the doped silicon oxide with a gas-phase etch which retains material in the alternating silicon oxide and silicon nitride slabs in each of the top portion and the bottom portion. The bottom portion and the top portion of the compound stack are fluidly coupled and the top portion is laterally displaced from the bottom portion.

The top portion may be displaced from the bottom portion by at least 5 nm. The bottom portion may include at least twenty pairs of slabs. The top portion may include at least twenty pairs of slabs. The doped silicon oxide may be doped with boron. The doped silicon oxide may be doped with phosphorus.

Additional embodiments and features are set forth in part in the description that follows, and in part will become apparent to those skilled in the art upon examination of the specification or may be learned by the practice of the disclosed embodiments. The features and advantages of the disclosed embodiments may be realized and attained by means of the instrumentalities, combinations, and methods described in the specification.

DESCRIPTION OF THE DRAWINGS

A further understanding of the nature and advantages of the embodiments may be realized by reference to the remaining portions of the specification and the drawings.

FIGS. 1A-1I are cross-sectional views of a patterned substrate during formation of a 3-d flash memory according to embodiments.

FIG. 2 is a flow chart of process for forming 3-d flash memory according to embodiments.

FIGS. 3A-3J are cross-sectional views of a patterned substrate during formation of a 3-d flash memory according to embodiments.

FIG. 4 is a flow chart of process for forming 3-d flash memory according to embodiments.

FIG. 5A shows a schematic cross-sectional view of a substrate processing chamber according to embodiments.

FIG. 5B shows a schematic cross-sectional view of a portion of a substrate processing chamber according to embodiments.

FIG. 5C shows a bottom plan view of a showerhead according to embodiments.

FIG. 6 shows a top plan view of an exemplary substrate processing system according to embodiments.

In the appended figures, similar components and/or features may have the same reference label. Further, various components of the same type may be distinguished by following the reference label by a dash and a second label that distinguishes among the similar components. If only the first reference label is used in the specification, the description is applicable to any one of the similar components having the same first reference label irrespective of the second reference label.

DETAILED DESCRIPTION

Methods of forming 3-d flash memory cells are described. The methods allow the cells to be produced despite a misalignment in at least two sections (top and bottom), each having multiple charge storage locations. The methods include selectively gas-phase etching dielectric from the bottom memory hole portion by delivering the etchants through the top memory hole. Two options for completing the methods include (1) forming a ledge spacer to allow reactive ion etching of the bottom polysilicon portion without damaging polysilicon or charge-trap/ONO layer on the ledge, and (2) placing sacrificial silicon oxide gapfill in the bottom memory hole, selectively forming protective conformal silicon nitride elsewhere, then removing the sacrificial silicon oxide gapfill before performing the reactive ion etching of the bottom polysilicon portion as before.

3-d flash memory (also referred to as VNAND) has entered production recently beginning with a relatively small number of layers. Storage capacity increases proportional to the number of layers. Beyond about forty to fifty layers the etch processes used to form the layers may become unreliable. Benefits of the disclosed embodiments disclosed herein include increasing the number of layers to form a compound memory hole having two or more portions vertically separated from one another. Overlay errors which arise in photolithography will displace the “bottom” portion from the “top” portion in the horizontal direction. Horizontal displacement can make further processing difficult for directional techniques such as reactive ion etching. A benefit of the processes described herein include tolerating misalignment which may enable lower cost manufacturing approaches compared to attempting to correct for the misalignment. The terms “bottom” and “top” will be used to describe any two neighboring portions of a 3-d flash memory even in situations where there are three, four or more portions of alternating silicon oxide and silicon nitride/tungsten slabs in a device. Each portion may be separated by a dielectric (e.g. silicon oxide) which is thicker than any of the slabs themselves. “Top” and “Up” will be used herein to describe portions/directions perpendicularly distal from the substrate plane and further away from the center of mass of the substrate in the perpendicular direction. “Vertical” will be used to describe items aligned in the “Up” direction towards the “Top”. Other similar terms may be used whose meanings will now be clear. The vertical memory hole may be circular as viewed from above.

The solutions presented herein involve accommodating the reactive ion etch in a way that allows a working device to be formed. The approaches described herein are enabled, in part, by recently developed gas-phase etchants. Recently-developed gas-phase remote etch processes have been designed, in part, to remove the need to expose delicate surface patterns to liquid etchants. Liquid etchants are increasingly responsible for collapsing delicate surface patterns as linewidths are reduced. Liquid etchants also possess surface tension which make etchant penetration into the restricted spaces of compound memory holes difficult.

Reference is now made to FIGS. 1A-1I concurrently with references to FIG. 2. A method 201 of forming a 3-d flash memory cell is shown in FIG. 2. A method of forming a 3-d flash memory cell may involve forming a bottom portion of a compound stack of alternating silicon oxide 110 and silicon nitride 105 slabs and forming a bottom portion of a memory hole through the bottom portion of the compound stack. A memory hole may include between 30 and 90 pairs of slabs, between 35 and 75 pairs of slabs or between about 40 and about 60 pairs of slabs according to embodiments. The memory hole may have a width of between 350 Å and 3000 Å, between 500 Å and 2000 Å or between 700 Å and 1300 Å according to embodiments. The memory hole may have an aspect ratio (height to width) of between 15:1 and 50:1, between 20:1 and 40:1 or between 25:1 and 35:1 in embodiments. Several of the figures will show a smaller number of pairs to simplify the drawings and some will indicate a greater number of pairs of slabs through the use of ellipses.

The method may include filling the bottom portion of the compound stack with doped silicon oxide 190. The method may further include forming a top portion of the compound stack of alternating silicon oxide 106 and silicon nitride 111 slabs above the bottom portion and the sacrificial doped silicon oxide as shown in FIG. 1A. The method may further include forming a top portion of a memory hole through the top portion of the compound stack in operation 209 as shown in FIG. 1B. Operation 209 may involve reactive ion etching and exposes the sacrificial doped silicon oxide 190 which fills the bottom portion of the compound memory hole. The bottom portion and the top portion of the compound stack are fluidly coupled and the top portion is laterally displaced from the bottom portion by at least 5 nm, at least 7.5 nm or at least 10 nm.

The method may further include selectively removing the doped silicon oxide 190 with a gas-phase etch which retains material in the alternating silicon oxide and silicon nitride slabs in each of the top portion and the bottom portion in operation 210 (see FIG. 1C). The doped silicon oxide 190 may be doped with boron and/or phosphorus. A gas-phase etch is available from Applied Materials (Selectra™) which selectively removes doped silicon oxide while retaining silicon oxide (undoped) and silicon nitride as described in the course of describing exemplary equipment herein. Operations 209-210 may be used to form the misaligned compound memory hole used for all processes described herein. Operations 209-210 may also be performed separately according to embodiments.

The misaligned memory hole is initially formed (in operations 209-210) as described previously using doped silicon oxide 190 gapfill. The patterned substrate includes a vertical stack of alternating silicon oxide (110-111) and silicon nitride (105-106) slabs and a vertical memory hole having sidewalls lined (during operation 220) with a conformal ONO layer 125 as shown in FIG. 1D. The conformal ONO layer 125 may include a first silicon oxide layer 126, a silicon nitride layer 127 and a second silicon oxide layer 128 as shown in a blow-up view in FIG. 11. The thickness of conformal ONO layer 125 may be between 20 ⊂ and 100 Å, between 25 Å and 80 Å or between 30 Å and 60 Å according to embodiments. The patterned substrate further includes a first polysilicon layer 130 formed 230 on the conformal ONO layer 125 (see FIG. 1E). The vertical stack comprises a bottom portion and a top portion laterally misaligned the amounts described previously to form a ledge. The method further includes forming 240 a silicon nitride spacer 135 on the ledge as shown in FIG. 1F. The silicon nitride spacer 135 may be formed by depositing a low conformality spacer to reduce deposition of silicon nitride in the bottom portion. The low conformality spacer may then be etched back to leave the silicon nitride spacer 135 as with conventional spacer depositions. The method further includes removing a bottom portion of the first polysilicon layer 130-1 by reactive ion etching 250 the bottom portion of the first polysilicon layer (see FIG. 1G) while retaining sidewall portions of the first polysilicon layer. The presence of the silicon nitride spacer 135 on the ledge protects horizontal portions of the first polysilicon layer 130 other than the bottom portion 130-1. In the absence of the silicon nitride spacer 135, the horizontal portion of the first polysilicon layer near the center of the compound memory hole may be undesirably damaged or removed in embodiments.

The method further includes removing (in operation 270) a bottom portion 125-1 of the conformal ONO layer using a gas-phase etch (see FIG. 1H). The bottom portion 125-1 may include only the horizontal portion of the conformal ONO layer located at the bottom of the memory hole according to embodiments. The bottom portion 125-1 may consist of the entire horizontal portion of the conformal ONO layer 125 disposed at the bottom of the compound memory hole in embodiments. A high temperature SiCoNi etch (also available from Applied Materials, Santa Clara, Calif.) has been found to remove both the silicon oxide and silicon nitride layers of the conformal ONO layer without requiring sublimation. Another gas phase etch or sequence of etches may be used, for example, to selectively remove silicon oxide then silicon nitride and then silicon oxide again to complete the process (a Selectra chamber discussed below may be used in this case). The gas phase etch process removes the bottom portion 125-1 and exposes the underlying silicon to improve the electrical connection made by the second polysilicon layer in a subsequent step. The method further includes removing the silicon nitride spacer from the ledge using a gas-phase etch 260 which may occur before or after operation 270. The method further includes forming (operation 280) a second polysilicon layer 131 on the first polysilicon layer 130 and making electrical contact between the first polysilicon layer 130, the second polysilicon layer 131 and the underlying silicon 101 as shown in FIG. 11.

Removing the bottom portion of the conformal ONO layer may be performed by exciting a hydrogen-containing precursor and a fluorine-containing precursor in a remote plasma to form plasma effluents in a SiCoNi etch process in embodiments. The plasma effluents may be flowed into a substrate processing region through a showerhead. The patterned substrate is in the substrate processing region and a temperature of the patterned substrate may be greater than 95° C. so no sublimation is necessary according to embodiments.

Reference is now made to FIGS. 3A-3J concurrently with references to FIG. 4. A method of forming a 3-d flash memory cell is shown 401 in FIG. 4. The misaligned memory hole is initially formed 410 as described previously (with reference to FIG. 2) using doped silicon oxide 390 gapfill (see FIGS. 3A-3C). Aspects of the process of FIG. 2 may not be repeated in this discussion for the sake of brevity. Furthermore, details of the process of FIG. 4 may be combined in the process of FIG. 2 in embodiments. The patterned substrate includes a vertical stack of alternating silicon oxide (310-311) and silicon nitride (305-306) slabs and a vertical memory hole having sidewalls lined (operation 420) with a conformal ONO layer 325 as shown in FIG. 3D. A memory hole may include between 30 and 90 pairs of slabs, between 35 and 75 pairs of slabs or between about 40 and about 60 pairs of slabs according to embodiments. Several of the figures will show a smaller number of pairs to simplify the drawings and some will indicate a greater number of pairs of slabs through the use of ellipses.

The conformal ONO layer 325 may include a first silicon oxide layer, a silicon nitride layer and a second silicon oxide layer as shown in FIG. 3D. The patterned substrate further includes a first polysilicon layer 330 formed (operation 430) on the conformal ONO layer 325 (see FIG. 3E). The vertical stack comprises a bottom portion and a top portion laterally misaligned in amounts described elsewhere herein to form a ledge. The method further includes forming a sacrificial silicon oxide gapfill 336 in the bottom portion of the misaligned memory hole in operation 440 as shown in FIG. 3F. Forming the sacrificial silicon oxide gapfill 336 may include etching back the sacrificial silicon oxide gapfill 336 to the desired height. Conformal silicon nitride 337 is selectively formed only on portions of the first polysilicon layer 330 which are exposed or uncovered by sacrificial silicon oxide gapfill 336 in operation 445 as shown in FIG. 3G. In embodiments, the surface of the polysilicon may be treated to encourage the selective deposition of the conformal silicon nitride 337 on the first polysilicon layer 330 rather than on the sacrificial silicon oxide gapfill 336. The sacrificial silicon oxide gapfill 336 has served its purpose at this point and is removed in operation 450 (using e.g. a selective silicon oxide Selectra etch). The method further includes removing a bottom portion of the first polysilicon layer 330-1 by reactive ion etching 460 the bottom portion of the first polysilicon layer while retaining sidewall portions of the first polysilicon layer. The silicon nitride may withstand the reactive ion etching whereas the polysilicon may not. The horizontal portion of the silicon nitride 337 near the center of the memory hole may protect the horizontal polysilicon portion on the ledge while beneficially allowing the bottom polysilicon portion 330-1 to be removed. The horizontal portion of the silicon nitride 337 may abut the horizontal portion of the polysilicon 330 on the ledge according to embodiments. The resulting structure is shown in FIG. 3H. In the absence of the conformal silicon nitride 137, the horizontal portion of the first polysilicon layer near the center of the compound memory hole may be undesirably damaged or removed in embodiments.

The method further includes removing (in operation 470) a bottom portion 325-1 of the conformal ONO layer using a gas-phase etch as shown in FIG. 3I. A high temperature SiCoNi etch has been found to remove both the silicon oxide and silicon nitride layers of the conformal ONO layer without requiring sublimation. SiCoNi also exposes the underlying silicon to improve the electrical connection made by the second polysilicon layer in a subsequent step. The method further includes forming (in operation 480) a second polysilicon layer 331 on the first polysilicon layer 330 and making electrical contact between the first polysilicon layer 330, the second polysilicon layer 331 and the underlying silicon 301.

Removing the bottom portion of the conformal ONO layer 325-1 may be performed by exciting a hydrogen-containing precursor and a fluorine-containing precursor in a remote plasma to form plasma effluents. The plasma effluents may be flowed into a substrate processing region through a showerhead. During an exemplary SiCoNi (Applied Materials) process, the patterned substrate is in the substrate processing region and a temperature of the patterned substrate may be maintained at more than 95° C. so no solid residue is formed which may stress the memory hole structure. In high temperature SiCoNi processes, no sublimation operation may be necessary.

Hardware and processes may be selected to achieve the high etch selectivities which enable the aforementioned processes and devices. Additional detail about appropriate hardware and processes will now be presented. In embodiments, an ion suppressor (which may be the showerhead) may be used to provide radical and/or neutral species for gas-phase etching. The ion suppressor may also be referred to as an ion suppression element. In embodiments, for example, the ion suppressor is used to filter etching plasma effluents (including radical-fluorine) en route from the remote plasma region to the substrate processing region. The ion suppressor may be used to provide a reactive gas having a higher concentration of radicals than ions. Plasma effluents pass through the ion suppressor disposed between the remote plasma region and the substrate processing region. The ion suppressor functions to dramatically reduce or substantially eliminate ionic species traveling from the plasma generation region to the substrate. The ion suppressors described herein are simply one way to achieve a low electron temperature in the substrate processing region during the gas-phase etch processes described herein.

In embodiments, an electron beam is passed through the substrate processing region in a plane parallel to the substrate to reduce the electron temperature of the plasma effluents. A simpler showerhead may be used if an electron beam is applied in this manner. The electron beam may be passed as a laminar sheet disposed above the substrate in embodiments. The electron beam provides a source of neutralizing negative charge and provides a more active means for reducing the flow of positively charged ions towards the substrate and increasing the selectivity of silicon nitride in embodiments. The flow of plasma effluents and various parameters governing the operation of the electron beam may be adjusted to lower the electron temperature measured in the substrate processing region.

The electron temperature may be measured using a Langmuir probe in the substrate processing region during excitation of a plasma in the remote plasma. In embodiments, the electron temperature may be less than 0.5 eV, less than 0.45 eV, less than 0.4 eV, or less than 0.35 eV. These extremely low values for the electron temperature are enabled by the presence of the electron beam, showerhead and/or the ion suppressor. Uncharged neutral and radical species may pass through the electron beam and/or the openings in the ion suppressor to react at the substrate. Such a process using radicals and other neutral species can reduce plasma damage compared to conventional plasma etch processes that include sputtering and bombardment. Embodiments of the present invention are also advantageous over conventional wet etch processes where surface tension of liquids can cause bending and peeling of small features.

The substrate processing region may be described herein as “plasma-free” during the etch processes described herein. “Plasma-free” does not necessarily mean the region is devoid of plasma. Ionized species and free electrons created within the plasma region may travel through pores (apertures) in the partition (showerhead) at exceedingly small concentrations. The borders of the plasma in the chamber plasma region are hard to define and may encroach upon the substrate processing region through the apertures in the showerhead. Furthermore, a low intensity plasma may be created in the substrate processing region without eliminating desirable features of the etch processes described herein. All causes for a plasma having much lower intensity ion density than the chamber plasma region during the creation of the excited plasma effluents do not deviate from the scope of “plasma-free” as used herein.

FIG. 5A shows a cross-sectional view of an exemplary substrate processing chamber 1001 with partitioned plasma generation regions within the processing chamber. During film etching, e.g., silicon oxide or silicon nitride, etc., a process gas may be flowed into chamber plasma region 1015 through a gas inlet assembly 1005. A remote plasma system (RPS) 1002 may optionally be included in the system, and may process a first gas which then travels through gas inlet assembly 1005. The inlet assembly 1005 may include two or more distinct gas supply channels where the second channel (not shown) may bypass the RPS 1002, if included. Accordingly, in embodiments the precursor gases may be delivered to the processing chamber in an unexcited state. The process gas may be excited within the RPS 1002 prior to entering the chamber plasma region 1015. Accordingly, the fluorine-containing precursor as discussed above, for example, may pass through RPS 1002 or bypass the RPS unit in embodiments. Various other examples encompassed by this arrangement will be similarly understood.

A cooling plate 1003, faceplate 1017, ion suppressor 1023, showerhead 1025, and a substrate support 1065 (also known as a pedestal), having a substrate 1055 disposed thereon, are shown and may each be included according to embodiments. The pedestal 1065 may have a heat exchange channel through which a heat exchange fluid flows to control the temperature of the substrate. This configuration may allow the substrate 1055 temperature to be cooled or heated to maintain relatively low temperatures, such as between about −20° C. to about 200° C., or therebetween. The wafer support platter of the pedestal 1065 may also be resistively heated to relatively high temperatures, such as from up to or about 100° C. to above or about 1100° C.

In embodiments, the faceplate 1017 may be flat (as shown) and include a plurality of through-channels used to distribute process gases. Plasma generating gases and/or plasma excited species, depending on use of the RPS 1002, may pass through a plurality of holes, shown in FIG. 3B, in faceplate 1017 for a more uniform delivery into the chamber plasma region 1015.

Exemplary configurations may include having the gas inlet assembly 1005 open into a gas supply region 1058 partitioned from the chamber plasma region 1015 by faceplate 1017 so that the gases/species flow through the holes in the faceplate 1017 into the chamber plasma region 1015. Structural and operational features may be selected to prevent significant backflow of plasma from the chamber plasma region 1015 back into the supply region 1058, gas inlet assembly 1005, and fluid supply system 1010. The structural features may include the selection of dimensions and cross-sectional geometries of the apertures in faceplate 1017 to deactivate back-streaming plasma. The operational features may include maintaining a pressure difference between the gas supply region 1058 and chamber plasma region 1015 that maintains a unidirectional flow of plasma through the showerhead 1025. The faceplate 1017, or a conductive top portion of the chamber, and showerhead 1025 are shown with an insulating ring 1020 located between the features, which allows an AC potential to be applied to the faceplate 1017 relative to showerhead 1025 and/or ion suppressor 1023. The insulating ring 1020 may be positioned between the faceplate 1017 and the showerhead 1025 and/or ion suppressor 1023 enabling a capacitively coupled plasma (CCP) to be formed in the first plasma region. A baffle (not shown) may additionally be located in the chamber plasma region 1015, or otherwise coupled with gas inlet assembly 1005, to affect the flow of fluid into the region through gas inlet assembly 1005.

The ion suppressor 1023 may comprise a plate or other geometry that defines a plurality of apertures throughout the structure that are configured to suppress the migration of ionically-charged species out of chamber plasma region 1015 while allowing uncharged neutral or radical species to pass through the ion suppressor 1023 into an activated gas delivery region between the suppressor and the showerhead. In embodiments, the ion suppressor 1023 may comprise a perforated plate with a variety of aperture configurations. These uncharged species may include highly reactive species that are transported with less reactive carrier gas through the apertures. As noted above, the migration of ionic species through the holes may be reduced, and in some instances completely suppressed. Controlling the amount of ionic species passing through the ion suppressor 1023 may provide increased control over the gas mixture brought into contact with the underlying wafer substrate, which in turn may increase control of the deposition and/or etch characteristics of the gas mixture. For example, adjustments in the ion concentration of the gas mixture can significantly alter its etch selectivity, e.g., SiO:Si etch ratios, SiN:Si etch ratios, etc.

The plurality of holes in the ion suppressor 1023 may be configured to control the passage of the activated gas, i.e., the ionic, radical, and/or neutral species, through the ion suppressor 1023. For example, the aspect ratio of the holes, or the hole diameter to length, and/or the geometry of the holes may be controlled so that the flow of ionically-charged species in the activated gas passing through the ion suppressor 1023 is reduced. The holes in the ion suppressor 1023 may include a tapered portion that faces chamber plasma region 1015, and a cylindrical portion that faces the showerhead 1025. The cylindrical portion may be shaped and dimensioned to control the flow of ionic species passing to the showerhead 1025. An adjustable electrical bias may also be applied to the ion suppressor 1023 as an additional means to control the flow of ionic species through the suppressor.

The ion suppression element 1023 may function to reduce or eliminate the amount of ionically charged species traveling from the plasma generation region to the substrate. Uncharged neutral and radical species may still pass through the openings in the ion suppressor to react with the substrate.

Showerhead 1025 in combination with ion suppressor 1023 may allow a plasma present in chamber plasma region 1015 to avoid directly exciting gases in substrate processing region 1033, while still allowing excited species to travel from chamber plasma region 1015 into substrate processing region 1033. In this way, the chamber may be configured to prevent the plasma from contacting a substrate 1055 being etched. This may advantageously protect a variety of intricate structures and films patterned on the substrate, which may be damaged, dislocated, or otherwise warped if directly contacted by a generated plasma. Additionally, when plasma is allowed to contact the substrate or approach the substrate level, the etch selectivity may decrease.

The processing system may further include a power supply 1040 electrically coupled with the processing chamber to provide electric power to the faceplate 1017, ion suppressor 1023, showerhead 1025, and/or pedestal 1065 to generate a plasma in the chamber plasma region 1015 or processing region 1033. The power supply may be configured to deliver an adjustable amount of power to the chamber depending on the process performed. Such a configuration may allow for a tunable plasma to be used in the processes being performed. Unlike a remote plasma unit, which is often presented with on or off functionality, a tunable plasma may be configured to deliver a specific amount of power to chamber plasma region 1015. This in turn may allow development of particular plasma characteristics such that precursors may be dissociated in specific ways to enhance the etching profiles produced by these precursors.

A plasma may be ignited either in chamber plasma region 1015 above showerhead 1025 or substrate processing region 1033 below showerhead 1025 in processes where “plasma-free” is not necessary. A plasma may be present in chamber plasma region 1015 to produce the radical-fluorine precursors from an inflow of the fluorine-containing precursor. An AC voltage typically in the radio frequency (RF) range may be applied between the conductive top portion of the processing chamber, such as faceplate 1017, and showerhead 1025 and/or ion suppressor 1023 to ignite a plasma in chamber plasma region 1015 during deposition. An RF power supply may generate a high RF frequency of 13.56 MHz but may also generate other frequencies alone or in combination with the 13.56 MHz frequency.

Plasma power can be of a variety of frequencies or a combination of multiple frequencies. In the exemplary processing system the plasma may be provided by RF power delivered to faceplate 1017 relative to ion suppressor 1023 and/or showerhead 1025. The RF power may be between about 10 watts and about 5000 watts, between about 100 watts and about 2000 watts, between about 200 watts and about 1500 watts, or between about 200 watts and about 1000 watts in embodiments. The RF frequency applied in the exemplary processing system may be low RF frequencies less than about 200 kHz, high RF frequencies between about 10 MHz and about 15 MHz, or microwave frequencies greater than or about 1 GHz in embodiments. The plasma power may be capacitively-coupled (CCP) or inductively-coupled (ICP) into the remote plasma region.

Excited effluents including radical fluorine formed from a fluorine-containing precursor, may be flowed into the processing region 1033 by embodiments of the showerhead described herein. Excited species derived from the process gas in chamber plasma region 1015 may travel through apertures in the ion suppressor 1023, and/or showerhead 1025 and react with an additional precursor flowing into the processing region 1033 from a separate portion of the showerhead. Alternatively, if all precursor species are being excited in chamber plasma region 1015, no additional precursors may be flowed through the separate portion of the showerhead. Little or no plasma may be present in the processing region 1033 during the remote plasma etch process in embodiments. Excited derivatives of the precursors may combine in the region above the substrate and/or on the substrate to etch structures or remove species from the substrate.

Some dry-etch processes involve the exposure of a substrate to remote plasma by-products formed from one or more precursors. Secondary precursors may be introduced directly into the substrate processing region without passing through the remote plasma. Selection of precursors results in an etch process which is selective of a specific material. For example, remote plasma generation of a fluorine precursor in combination with an oxygen precursor results in a selective etch of silicon nitride. In contrast, a remote plasma generation of a fluorine precursor and concurrent introduction of moisture directly into the substrate processing region results in a selective etch of silicon oxide at about room temperature. Doped silicon oxide may be selectively removed by combining radical-fluorine with moisture (by-passing any plasma excitation) and maintaining the substrate temperature at about 60° C. rather than near room temperature. Specific examples of precursors will now be presented. In embodiments intended to preferentially etch doped or undoped silicon oxide, the fluorine-containing precursor may be nitrogen trifluoride and the secondary precursor (excited only by the radical-fluorine) may be water vapor (H₂O). Water vapor, when used, may be delivered using a mass flow meter (MFM), an injection valve, or by commercially available water vapor generators. Gaseous precursors may be delivered using mass flow controllers (MFC's). In embodiments intended to preferentially etch silicon nitride, the fluorine-containing precursor may be nitrogen trifluoride which may be combined with a second precursor and the mixture may be excited in a remote plasma. The second precursor in the mixture may be oxygen (O₂) or another oxygen-containing precursor. In embodiments intended to preferentially etch silicon (e.g. polysilicon), the fluorine-containing precursor may be nitrogen trifluoride which may be combined with a second precursor and the mixture may be excited in a remote plasma. The second precursor in the mixture may be hydrogen (H₂). Other combinations of precursors have been developed for each of the selective etches used herein, however, the combinations described are sufficient to enable the process flows.

FIG. 5B shows a detailed view of the features affecting the processing gas distribution through faceplate 1017. As shown in FIG. 5A and FIG. 5B, faceplate 1017, cooling plate 1003, and gas inlet assembly 1005 intersect to define a gas supply region 1058 into which process gases may be delivered from gas inlet 1005. The gases may fill the gas supply region 1058 and flow to chamber plasma region 1015 through apertures 1059 in faceplate 1017. The apertures 1059 may be configured to direct flow in a substantially unidirectional manner such that process gases may flow into processing region 1033, but may be partially or fully prevented from backflow into the gas supply region 1058 after traversing the faceplate 1017.

The gas distribution assemblies such as showerhead 1025 for use in the processing chamber section 1001 may be referred to as dual channel showerheads (DCSH) and are additionally detailed in the embodiments described in FIG. 5A as well as FIG. 5C herein. The dual channel showerhead may provide for etching processes that allow for separation of etchants outside of the processing region 1033 to provide limited interaction with chamber components and each other prior to being delivered into the processing region.

The showerhead 1025 may comprise an upper plate 1014 and a lower plate 1016. The plates may be coupled with one another to define a volume 1018 between the plates. The coupling of the plates may be so as to provide first fluid channels 1019 through the upper and lower plates, and second fluid channels 1021 through the lower plate 1016. The formed channels may be configured to provide fluid access from the volume 1018 through the lower plate 1016 via second fluid channels 1021 alone, and the first fluid channels 1019 may be fluidly isolated from the volume 1018 between the plates and the second fluid channels 1021. The volume 1018 may be fluidly accessible through a side of the gas distribution assembly 1025. Although the exemplary system of FIGS. 5A-5C includes a dual-channel showerhead, it is understood that alternative distribution assemblies may be utilized that maintain first and second precursors fluidly isolated prior to the processing region 1033. For example, a perforated plate and tubes underneath the plate may be utilized, although other configurations may operate with reduced efficiency or not provide as uniform processing as the dual-channel showerhead as described.

In the embodiment shown, showerhead 1025 may distribute via first fluid channels 1019 process gases which contain plasma effluents upon excitation by a plasma in chamber plasma region 1015. In embodiments, the process gas introduced into the RPS 1002 and/or chamber plasma region 1015 may contain fluorine, e.g., CF₄, NF₃ or XeF₂. The process gas may also include a carrier gas such as helium, argon, nitrogen (N₂), etc. Plasma effluents may include ionized or neutral derivatives of the process gas and may also be referred to herein as a radical-fluorine precursor referring to the atomic constituent of the process gas introduced.

FIG. 5C is a bottom view of a showerhead 1025 for use with a processing chamber in embodiments. Showerhead 1025 corresponds with the showerhead shown in FIG. 5A. Through-holes 1031, which show a view of first fluid channels 1019, may have a plurality of shapes and configurations to control and affect the flow of precursors through the showerhead 1025. Small holes 1027, which show a view of second fluid channels 1021, may be distributed substantially evenly over the surface of the showerhead, even amongst the through-holes 1031, which may help to provide more even mixing of the precursors as they exit the showerhead than other configurations.

The chamber plasma region 1015 or a region in an RPS may be referred to as a remote plasma region. In embodiments, the radical precursor, e.g., a radical-fluorine precursor, is created in the remote plasma region and travels into the substrate processing region where it may or may not combine with additional precursors. In embodiments, the additional precursors are excited only by the radical-fluorine precursor. Plasma power may essentially be applied only to the remote plasma region in embodiments to ensure that the radical-fluorine precursor provides the dominant excitation.

Combined flow rates of precursors into the chamber may account for 0.05% to about 20% by volume of the overall gas mixture; the remainder being carrier gases. The fluorine-containing precursor may be flowed into the remote plasma region, but the plasma effluents may have the same volumetric flow ratio in embodiments. In the case of the fluorine-containing precursor, a purge or carrier gas may be first initiated into the remote plasma region before the fluorine-containing gas to stabilize the pressure within the remote plasma region. Substrate processing region 1033 can be maintained at a variety of pressures during the flow of precursors, any carrier gases, and plasma effluents into substrate processing region 1033. The pressure may be maintained between about 0.1 mTorr and about 100 Torr, between about 1 Torr and about 20 Torr or between about 1 Torr and about 5 Torr in embodiments.

Embodiments of the deposition systems may be incorporated into larger fabrication systems for producing integrated circuit chips. FIG. 6 shows one such processing system (mainframe) 1101 of deposition, etching, baking, and curing chambers in embodiments. In the figure, a pair of front opening unified pods (load lock chambers 1102) supply substrates of a variety of sizes that are received by robotic arms 1104 and placed into a low pressure holding area 1106 before being placed into one of the substrate processing chambers 1108 a-f. A second robotic arm 1110 may be used to transport the substrate wafers from the holding area 1106 to the substrate processing chambers 1108 a-f and back. Each substrate processing chamber 1108 a-f, can be outfitted to perform a number of substrate processing operations including the dry etch processes described herein in addition to cyclical layer deposition (CLD), atomic layer deposition (ALD), chemical vapor deposition (CVD), physical vapor deposition (PVD), etch, pre-clean, degas, orientation, and other substrate processes.

The substrate processing chambers 1108 a-f may be configured for depositing, annealing, curing and/or etching a film on the substrate wafer. In one configuration, chambers 1108 a-b, may be configured to etch silicon nitride, chambers 1108 c-d may be configured to etch silicon oxide, and chambers 1108 e-f may be configured to etch silicon.

In the preceding description, for the purposes of explanation, numerous details have been set forth to provide an understanding of various embodiments of the present invention. It will be apparent to one skilled in the art, however, that certain embodiments may be practiced without some of these details, or with additional details.

As used herein “substrate” may be a support substrate with or without layers formed thereon. The patterned substrate may be an insulator or a semiconductor of a variety of doping concentrations and profiles and may, for example, be a semiconductor substrate of the type used in the manufacture of integrated circuits. Exposed “silicon” or “polysilicon” of the patterned substrate is predominantly Si but may include minority concentrations of other elemental constituents such as nitrogen, oxygen, hydrogen and carbon. Exposed “silicon” or “polysilicon” may consist of or consist essentially of silicon. Exposed “silicon nitride” of the patterned substrate is predominantly Si₃N₄ but may include minority concentrations of other elemental constituents such as oxygen, hydrogen and carbon. “Exposed silicon nitride” may consist essentially of or consist of silicon and nitrogen. Exposed “silicon oxide” of the patterned substrate is predominantly SiO₂ but may include minority concentrations of other elemental constituents such as nitrogen, hydrogen and carbon. In embodiments, silicon oxide films etched using the methods taught herein consist essentially of or consist of silicon and oxygen.

The term “precursor” is used to refer to any process gas which takes part in a reaction to either remove material from or deposit material onto a surface. “Plasma effluents” describe gas exiting from the chamber plasma region and entering the substrate processing region. Plasma effluents are in an “excited state” wherein at least some of the gas molecules are in vibrationally-excited, dissociated and/or ionized states. A “radical precursor” is used to describe plasma effluents (a gas in an excited state which is exiting a plasma) which participate in a reaction to either remove material from or deposit material on a surface. “Radical-fluorine” are radical precursors which contain fluorine but may contain other elemental constituents. The phrase “inert gas” refers to any gas which does not form chemical bonds when etching or being incorporated into a film. Exemplary inert gases include noble gases but may include other gases so long as no chemical bonds are formed when (typically) trace amounts are trapped in a film.

The terms “gap” and “trench” are used throughout with no implication that the etched geometry has a large horizontal aspect ratio. Viewed from above the surface, trenches may appear circular, oval, polygonal, rectangular, or a variety of other shapes. A trench may be in the shape of a moat around an island of material. The term “via” is used to refer to a low aspect ratio trench (as viewed from above) which may or may not be filled with metal to form a vertical electrical connection. As used herein, an isotropic or a conformal etch process refers to a generally uniform removal of material on a surface in the same shape as the surface, i.e., the surface of the etched layer and the pre-etch surface are generally parallel. A person having ordinary skill in the art will recognize that the etched interface likely cannot be 100% conformal and thus the term “generally” allows for acceptable tolerances.

Having disclosed several embodiments, it will be recognized by those of skill in the art that various modifications, alternative constructions, and equivalents may be used without departing from the spirit of the disclosed embodiments. Additionally, a number of well-known processes and elements have not been described to avoid unnecessarily obscuring the present invention. Accordingly, the above description should not be taken as limiting the scope of the invention.

Where a range of values is provided, it is understood that each intervening value, to the tenth of the unit of the lower limit unless the context clearly dictates otherwise, between the upper and lower limits of that range is also specifically disclosed. Each smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in that stated range is encompassed. The upper and lower limits of these smaller ranges may independently be included or excluded in the range, and each range where either, neither or both limits are included in the smaller ranges is also encompassed within the invention, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

As used herein and in the appended claims, the singular forms “a”, “an”, and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a process” includes a plurality of such processes and reference to “the dielectric material” includes reference to one or more dielectric materials and equivalents thereof known to those skilled in the art, and so forth.

Also, the words “comprise,” “comprising,” “include,” “including,” and “includes” when used in this specification and in the following claims are intended to specify the presence of stated features, integers, components, or steps, but they do not preclude the presence or addition of one or more other features, integers, components, steps, acts, or groups. 

1. A method of forming a memory cell, the method comprising: forming a silicon nitride spacer on a ledge of a patterned substrate positioned in a substrate processing chamber, wherein the patterned substrate comprises a vertical stack of alternating oxide and nitride layers defining a vertical memory hole there through, wherein sidewalls of the vertical memory hole include a conformal coating and a first polysilicon layer overlying the conformal coating, and wherein the vertical stack comprises a bottom portion and a top portion laterally misaligned to form the ledge; removing a bottom portion of the first polysilicon layer by reactive ion etching the bottom portion of the first polysilicon layer while retaining sidewall portions of the first polysilicon layer; removing a bottom portion of the conformal coating using a gas-phase etch; removing the silicon nitride spacer from the ledge using a gas-phase etch; and forming a second polysilicon layer on the first polysilicon layer.
 2. The method of claim 1, wherein the conformal coating comprises a first silicon oxide layer, a silicon nitride layer, and a second silicon oxide layer.
 3. The method of claim 1, wherein the silicon nitride spacer completely covers the ledge while maintaining a line-of-sight path from top to bottom of the vertical memory hole.
 4. The method of claim 1, wherein forming the second polysilicon layer comprises making electrical contact between the first polysilicon layer, the second polysilicon layer and underlying silicon.
 5. The method of claim 1, wherein removing the silicon nitride spacer comprises exciting both a fluorine precursor and an oxygen precursor in a remote plasma to produce plasma effluents, and flowing the plasma effluents into a substrate processing region housing the patterned substrate.
 6. The method of claim 1, wherein the bottom portion and the top portion are laterally misaligned by more than 5 nm.
 7. The method of claim 1, wherein removing the bottom portion of the conformal coating is performed by exciting a hydrogen-containing precursor and a fluorine-containing precursor in a remote plasma to form plasma effluents.
 8. The method of claim 7, wherein the plasma effluents are flowed into a substrate processing region through a showerhead, wherein the patterned substrate is positioned in the substrate processing region, and wherein a temperature of the patterned substrate is greater than 95° C.
 9. A method of forming a memory cell, the method comprising: forming sacrificial silicon oxide in a bottom portion of a vertical memory hole through a patterned substrate in a substrate processing chamber, wherein the patterned substrate comprises a vertical stack of alternating oxide and nitride layers defining the vertical memory hole, wherein sidewalls of the vertical memory hole include an inner layer coating, wherein the patterned substrate further comprises a first polysilicon layer formed on the inner layer coating; wherein the vertical stack comprises the bottom portion and a top portion laterally misaligned to form a ledge; forming conformal silicon nitride on exposed portions of the first polysilicon layer exposed by the sacrificial silicon oxide; removing the sacrificial silicon oxide; removing a bottom portion of the first polysilicon layer by reactive ion etching the bottom portion of the first polysilicon layer while retaining sidewall portions of the first polysilicon layer; removing a bottom portion of the inner layer coating using a gas-phase etch; removing the conformal silicon nitride; and forming a second polysilicon layer on the first polysilicon layer producing electrical contact between the second polysilicon layer and underlying silicon.
 10. The method of claim 9, wherein the inner layer coating comprises a conformal coating.
 11. The method of claim 10, wherein the conformal coating comprises a first silicon oxide layer, a silicon nitride layer, and a second silicon oxide layer.
 12. The method of claim 9, wherein the bottom portion and the top portion are laterally misaligned by more than 5 nm.
 13. The method of claim 9, wherein removing the conformal silicon nitride comprises exciting both a fluorine precursor and an oxygen precursor in a remote plasma to produce plasma effluents, and flowing the plasma effluents into a substrate processing region housing the patterned substrate.
 14. The method of claim 13, wherein the fluorine precursor comprises nitrogen trifluoride and the oxygen precursor comprises molecular oxygen (O₂).
 15. A method of forming a memory cell, the method comprising: forming a bottom portion of a compound stack of alternating silicon oxide and silicon nitride slabs; forming a bottom portion of a memory hole through the bottom portion of the compound stack by patterning the bottom portion of the compound stack; filling the bottom portion of the compound stack with doped silicon oxide; forming a top portion of the compound stack of alternating silicon oxide and silicon nitride slabs; forming a top portion of a memory hole through the top portion of the compound stack by patterning the top portion of the compound stack and exposing the doped silicon oxide; and selectively removing the doped silicon oxide with a gas-phase etch which retains material in the alternating silicon oxide and silicon nitride slabs in each of the top portion and the bottom portion, wherein the bottom portion and the top portion of the compound stack are fluidly coupled and the top portion is laterally displaced from the bottom portion.
 16. The method of claim 15, wherein the top portion is displaced from the bottom portion by at least 5 nm.
 17. The method of claim 15, wherein the bottom portion comprises at least twenty pairs of slabs.
 18. The method of claim 15, wherein the top portion comprises at least twenty pairs of slabs.
 19. The method of claim 15, wherein the doped silicon oxide is doped with boron and/or phosphorus. 